JP5951568B2 - Semiconductor device and manufacturing method thereof - Google Patents

Semiconductor device and manufacturing method thereof Download PDF

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JP5951568B2
JP5951568B2 JP2013178713A JP2013178713A JP5951568B2 JP 5951568 B2 JP5951568 B2 JP 5951568B2 JP 2013178713 A JP2013178713 A JP 2013178713A JP 2013178713 A JP2013178713 A JP 2013178713A JP 5951568 B2 JP5951568 B2 JP 5951568B2
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JP2015050209A (en
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達朗 斎藤
達朗 斎藤
和田　真
真 和田
厚伸 磯林
厚伸 磯林
明広 梶田
明広 梶田
久生 宮崎
久生 宮崎
酒井　忠司
忠司 酒井
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    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
    • H01L21/76877—Filling of holes, grooves or trenches, e.g. vias, with conductive material
    • H—ELECTRICITY
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    • H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
    • H01L23/5226—Via connections in a multilevel interconnection structure
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    • H01L23/00—Details of semiconductor or other solid state devices
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    • H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
    • H01L23/532—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body characterised by the materials
    • H01L23/53204—Conductive materials
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
    • H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
    • H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
    • H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table
    • H01L21/28556—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD
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    • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
    • H01L2221/10—Applying interconnections to be used for carrying current between separate components within a device
    • H01L2221/1068—Formation and after-treatment of conductors
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Description

本発明の実施形態は、カーボンナノチューブ（以下、ＣＮＴと称す）をコンタクトビアに用いた半導体装置及びその製造方法に関する。   Embodiments described herein relate generally to a semiconductor device using a carbon nanotube (hereinafter referred to as CNT) as a contact via and a method for manufacturing the same.

近年、半導体装置の多層配線のビアホール内にカーボンナノチューブ（ＣＮＴ）を形成することにより、配線抵抗の低減をはかる方法が提案されている。ＣＮＴは、その量子化伝導特性により金属配線に替わるＬＳＩ用低抵抗配線として使用することが期待できる。さらに、ＣＮＴの構造が筒状であり、ＣＶＤ法にて垂直に成膜することが可能であることから、従来のデバイスの縦方向配線形成プロセスと優れた整合性を持つ。   In recent years, a method for reducing wiring resistance by forming carbon nanotubes (CNT) in via holes of a multilayer wiring of a semiconductor device has been proposed. CNT can be expected to be used as a low-resistance wiring for LSIs that replaces metal wiring due to its quantized conduction characteristics. Furthermore, since the structure of the CNT is cylindrical and can be formed vertically by the CVD method, it has excellent consistency with the vertical wiring formation process of the conventional device.

このように、ＣＮＴは縦方向配線として優れた電気特性を期待される新規材料であり、特に長距離配線において低抵抗な配線を実現する可能性がある。他方、ＣＮＴをコンタクトに適用するためには、バリスティック（Ballistic）長を長くするための施策が重要になる。例えば、ＣＮＴ中にＢｒやＮ等の元素をドーピングして、輸送されるキャリアを増加させる施策が挙げられる。   Thus, CNT is a novel material that is expected to have excellent electrical characteristics as a vertical wiring, and there is a possibility of realizing a low resistance wiring particularly in a long distance wiring. On the other hand, in order to apply CNT to the contact, a measure for increasing the ballistic length becomes important. For example, a measure for increasing the number of carriers to be transported by doping elements such as Br and N into CNTs.

特開２０１１−２０４７６９号公報JP 2011-204769 A

発明が解決しようとする課題は、中空構造のＣＮＴに安定して元素ドーピングを行うことができ、ＣＮＴを用いた配線の更なる低抵抗化をはかり得る半導体装置及びその製造方法を提供することである。   The problem to be solved by the present invention is to provide a semiconductor device capable of stably performing element doping on a hollow CNT and capable of further reducing the resistance of the wiring using the CNT, and a method for manufacturing the same. is there.

実施形態の半導体装置は、基板上に設けられ、配線接続のためのコンタクトビア用溝が形成された層間絶縁膜と、前記コンタクトビア用溝の底面に形成されたＣＮＴ成長のための触媒層と、前記触媒層が形成された前記コンタクトビア用溝内に複数本のＣＮＴを埋め込んで形成されたＣＮＴビアと、を具備している。そして、前記ＣＮＴは、複数のグラフェン層を前記コンタクトビア用溝の深さ方向から傾けた状態で積層して形成され、且つ前記コンタクトビア用溝の側壁に前記グラフェン層の末端が露出するように形成され、前記ＣＮＴ中に少なくとも１種類の元素が含まれている。 The semiconductor device of the embodiment includes an interlayer insulating film provided on a substrate and formed with contact via grooves for wiring connection, and a catalyst layer for CNT growth formed on the bottom surface of the contact via grooves. And a CNT via formed by embedding a plurality of CNTs in the contact via groove in which the catalyst layer is formed. The CNTs are formed by laminating a plurality of graphene layers in a state inclined from the depth direction of the contact via grooves , and the ends of the graphene layers are exposed on the side walls of the contact via grooves. is formed, it includes at least one element in the CNT.

第１の実施形態に係わる半導体装置の概略構成を示す断面図。1 is a cross-sectional view illustrating a schematic configuration of a semiconductor device according to a first embodiment. 図１の半導体装置に用いたＣＮＴの拡大構成及び元素ドーピングの様子を示す模式図。The schematic diagram which shows the mode of the expanded structure and element doping of CNT used for the semiconductor device of FIG. グラフェンの線幅と体積抵抗率との関係を示す図。The figure which shows the relationship between the line | wire width of graphene, and volume resistivity. グラフェンに対する元素ドーピングの例を示す図。The figure which shows the example of the element doping with respect to a graphene. ＣＮＴに対する元素ドーピングの例を示す図。The figure which shows the example of the element doping with respect to CNT. 第２の実施形態に係わる半導体装置の製造工程を示す断面図。Sectional drawing which shows the manufacturing process of the semiconductor device concerning 2nd Embodiment. 第２の実施形態に係わる半導体装置の製造工程を示す断面図。Sectional drawing which shows the manufacturing process of the semiconductor device concerning 2nd Embodiment.

以下、実施形態の半導体装置及びその製造方法を、図面を参照して説明する。   Hereinafter, a semiconductor device and a manufacturing method thereof according to embodiments will be described with reference to the drawings.

（第１の実施形態）
図１は、第１の実施形態に係わる半導体装置の概略構成を示す断面図である。 (First embodiment)
FIG. 1 is a cross-sectional view showing a schematic configuration of the semiconductor device according to the first embodiment.

本実施形態は、トランジスタやキャパシタ等の半導体素子が形成された基板上に、半導体素子と配線層又は配線層間を接続するためのコンタクト層が形成され、コンタクト層材料にＣＮＴビアを用いた構造である。さらに、少なくとも１種類以上の元素をドーピングした、グラフェン壁末端がＣＮＴ層側壁に露出したＣＮＴをコンタクトに適用した構造である。   In this embodiment, a contact layer for connecting a semiconductor element and a wiring layer or a wiring layer is formed on a substrate on which a semiconductor element such as a transistor or a capacitor is formed, and a CNT via is used as a contact layer material. is there. Furthermore, the structure is such that CNT doped with at least one element and having a graphene wall end exposed on the side wall of the CNT layer is applied to the contact.

図中の１０はトランジスタやキャパシタ等の素子が形成されたＳｉ基板（半導体基板）であり、この基板１０上にストッパ絶縁膜として機能するＳｉＯ2 ，ＳｉＯＣ等のキャップ層１１及びＳｉＯ2 等の配線層絶縁膜１２が形成されている。そして、絶縁膜１２に配線溝が形成され、配線溝内に金属膜を埋め込んで下層配線１５が形成されている。 In the figure, reference numeral 10 denotes an Si substrate (semiconductor substrate) on which elements such as transistors and capacitors are formed. A cap layer 11 such as SiO 2 and SiOC that functions as a stopper insulating film on the substrate 10 and wiring such as SiO 2. A layer insulating film 12 is formed. A wiring groove is formed in the insulating film 12, and a lower layer wiring 15 is formed by embedding a metal film in the wiring groove.

なお、キャップ層１１及び後述するキャップ層２１，４１は、下地の絶縁膜がＲＩＥダメージに強い膜、例えばＴＥＯＳや微小空孔を含まないＳｉＯＣ等の場合は、省略することも可能である。   Note that the cap layer 11 and cap layers 21 and 41 to be described later can be omitted if the underlying insulating film is a film resistant to RIE damage, for example, SiOC that does not include TEOS or microvoids.

下層配線１５を形成した基板１０上に、ＳｉＮ等のキャップ層２１及びＳｉＯ2 等の層間絶縁膜２２が形成されている。下層配線１５上で層間絶縁膜２２には、コンタクト用溝２３が形成されている。 A cap layer 21 such as SiN and an interlayer insulating film 22 such as SiO 2 are formed on the substrate 10 on which the lower layer wiring 15 is formed. A contact trench 23 is formed in the interlayer insulating film 22 on the lower wiring 15.

コンタクト用溝２３内には、ＴｉやＴｉＮ等の補助触媒層３１及びＮｉやＣｏ等の触媒層３２を介して複数本のＣＮＴ３３が埋め込み形成され、これにより上下の配線層を接続するためのＣＮＴビア３０が構成されている。ここで、各々のＣＮＴ３３は、触媒層３２の底部から上側に成長している。   A plurality of CNTs 33 are embedded and formed in the contact groove 23 via an auxiliary catalyst layer 31 such as Ti or TiN and a catalyst layer 32 such as Ni or Co, thereby connecting the upper and lower wiring layers. A via 30 is configured. Here, each CNT 33 grows upward from the bottom of the catalyst layer 32.

上記のようにＣＮＴビア３０を形成した基板上に、ＳｉＮ等のキャップ層４１、ＳｉＯ2 等の絶縁膜４２及びＣｕ等の上層配線層４５が形成されている。 A cap layer 41 such as SiN, an insulating film 42 such as SiO 2, and an upper wiring layer 45 such as Cu are formed on the substrate on which the CNT via 30 is formed as described above.

なお、絶縁膜４２は、配線層絶縁膜と層間絶縁膜の積層であっても良いし、層間絶縁膜の単独であっても良い。積層の場合は、配線用溝を有する配線層絶縁膜を形成した後に溝内に金属膜を埋め込んで上層配線４５を形成し、その上に層間絶縁膜を形成する。単独の場合は、上層配線層４５を形成した後に、これを埋め込むように層間絶縁膜を形成すれば良い。   The insulating film 42 may be a laminate of a wiring layer insulating film and an interlayer insulating film, or may be a single interlayer insulating film. In the case of stacking, after forming a wiring layer insulating film having a wiring groove, a metal film is buried in the groove to form an upper layer wiring 45, and an interlayer insulating film is formed thereon. In the case of a single layer, after the upper wiring layer 45 is formed, an interlayer insulating film may be formed so as to be embedded.

触媒下地層３１はＣＮＴ層の形成を容易にするための補助膜であり、触媒層３２の絶縁膜及び下層コンタクト中への拡散を防止する。代表的な触媒下地層材料としてＴａ，Ｔｉ，Ｒｕ，Ｗ，Ａｌなどが挙げられる。また、これらの膜の窒化物や酸化物、更にはこれらの膜を含む積層材料も用いることが可能である。   The catalyst underlayer 31 is an auxiliary film for facilitating the formation of the CNT layer, and prevents diffusion of the catalyst layer 32 into the insulating film and the lower layer contact. Typical catalyst underlayer materials include Ta, Ti, Ru, W, Al, and the like. In addition, nitrides and oxides of these films, and laminated materials including these films can also be used.

触媒層３２はＣＮＴを形成するために必要な層であり、触媒材料にはＣｏ，Ｎｉ，Ｆｅ、Ｒｕ、Ｃｕなどの単体金属、又は少なくともこれらの何れかを含む合金、或いはこれらの炭化物等が好ましい。ＣＮＴの触媒層としては、分散状態となった不連続膜であることが望ましい。ここで、コンタクトビアに形成したＣＮＴを固定化する目的で、例えばＣＶＤ法により形成した絶縁膜や金属を埋め込んでも良い。   The catalyst layer 32 is a layer necessary for forming CNT, and the catalyst material is a single metal such as Co, Ni, Fe, Ru, Cu, an alloy containing at least one of these, or a carbide thereof. preferable. The CNT catalyst layer is preferably a discontinuous film in a dispersed state. Here, for the purpose of fixing the CNT formed in the contact via, for example, an insulating film or metal formed by a CVD method may be embedded.

また、図示しない拡散防止層（Diffusion Barrier）が配線構造を被覆するように成膜されてもよい。拡散防止層には、例えばＳｉＮなどが用いられる。また、用いるＣＮＴとしては、ＣＮＴ最外周にグラフェン壁が複数存在し、構成元素がＣ単体でないことを特徴とする。   Further, a diffusion barrier layer (not shown) may be formed so as to cover the wiring structure. For example, SiN is used for the diffusion preventing layer. In addition, the CNT to be used is characterized in that a plurality of graphene walls exist on the outermost periphery of the CNT and the constituent element is not C simple substance.

ＣＮＴビア３０の各々のＣＮＴ３３は、図２に示すように、複数のグラフェン層３３ａをコンタクトビア用溝２３の深さ方向から傾けた状態で積層して形成され、側壁にグラフェン層３３ａの末端が露出するカップスタック型に形成されている。一つのグラフェン層３３ａの高さは５ｎｍ以上となっている。そして、ＣＮＴ３３の側壁からグラフェン層３３ａに少なくとも１種類の元素５１がドーピングされている。   As shown in FIG. 2, each CNT 33 of the CNT via 30 is formed by laminating a plurality of graphene layers 33a in a state inclined from the depth direction of the contact via groove 23, and the end of the graphene layer 33a is formed on the side wall. It is formed in an exposed cup stack type. The height of one graphene layer 33a is 5 nm or more. The graphene layer 33a is doped with at least one element 51 from the side wall of the CNT 33.

ここで、グラフェンとはベンゼン環が平面状に規則的に並んだ膜が１〜１００層程度積層した極めて薄い炭素材料である。また、通常のＣＮＴは、ベンゼン環が平面上に規則的に並んだ膜の積層炭素材料であるグラフェンが直径１０〜１００ｎｍの筒状構造になっている炭素材料である。   Here, graphene is an extremely thin carbon material in which about 1 to 100 layers of films in which benzene rings are regularly arranged in a plane are stacked. Ordinary CNT is a carbon material in which graphene, which is a laminated carbon material of a film in which benzene rings are regularly arranged on a plane, has a cylindrical structure with a diameter of 10 to 100 nm.

本実施形態のように、グラフェン壁末端がＣＮＴ層側壁に露出したＣＮＴとしては、例えばカップスタック型のＣＮＴなどのように試験管のような形状のグラフェン層のスタック構造が挙げられる。その特徴としては、１層のグラフェン層がＣＮＴの末端から末端まで接続していないことに起因して単体ではバリスティック長が短く高抵抗になることが知られているが、ＣＮＴ層末端が側壁に位置するため、元素のドーピングパスがＣＮＴ側壁に存在する。また、構造の観点からはＣＮＴの長さ方向に広がることにより他元素が存在可能な安定位置を確保することが可能となる。   As in this embodiment, examples of the CNTs whose graphene wall ends are exposed on the side walls of the CNT layer include a stack structure of a graphene layer shaped like a test tube such as a cup stack type CNT. As its feature, it is known that a single graphene layer is not connected from the end to the end of the CNT, so that the ballistic length is short and high resistance by itself, but the end of the CNT layer is the side wall Therefore, an element doping path exists on the CNT side wall. Further, from the viewpoint of the structure, it is possible to secure a stable position where other elements can exist by spreading in the length direction of the CNT.

上記特性により、ＣＮＴ中に元素を十分にドーピングすることが可能であり、輸送されるキャリアを増加させることにより、コンタクトビアでの低抵抗化を実現できる構造である。また、プロセスの観点からはグラフェン壁末端がＣＮＴ層側壁に露出したＣＮＴは低温での成長が可能であり、多様なデバイスへの適用を可能とするプロセスを実現できる利点がある。   With the above characteristics, the CNT can be sufficiently doped with an element, and by increasing the number of transported carriers, the resistance can be reduced in the contact via. Further, from the viewpoint of the process, the CNT having the graphene wall end exposed on the side wall of the CNT layer can be grown at a low temperature, which has an advantage of realizing a process that can be applied to various devices.

図３は、グラフェンの体積抵抗率と線幅との関係を示す図であり、Ｂｒのドーピングによる低抵抗化を表している。ドーピング無しＡに比べドーピング有りＢでは、２桁ほど体積抵抗率が下がっている。   FIG. 3 is a graph showing the relationship between the volume resistivity and the line width of graphene, and shows a reduction in resistance by doping Br. In the case of B with doping, the volume resistivity is reduced by about two orders of magnitude compared with the case of A without doping.

グラフェンのドーピングに関しては、図４（ａ）に示すように基板６１上にグラフェン層６２を積層したものの場合、図４（ｂ）に示すように、横方向からＢｒをドーピングすることにより、グラフェン層６２の側壁や欠陥から原子５１が侵入し、グラフェン層間が広がり、抵抗を小さくすることができる。   Regarding the doping of graphene, in the case where the graphene layer 62 is laminated on the substrate 61 as shown in FIG. 4A, the graphene layer is obtained by doping Br from the lateral direction as shown in FIG. 4B. The atoms 51 enter from the side walls and defects of 62, and the graphene interlayer spreads, so that the resistance can be reduced.

一方、図５に示すように、中空構造のＣＮＴ６３の場合、先端からしか原子５１が侵入できないため、径が広がらずグラフェンと同様の低抵抗化をはかることは極めて困難である。即ち、中空構造のＣＮＴへの適用を行った場合、最外殻のＣＮＴ層以外へのドーピングパスとしてはＣＮＴの先端或いは外殻ＣＮＴの欠陥部分しかなく、ＣＮＴの径は殆ど広がらない。このため、安定してＣＮＴ中に元素ドーピングすることはできず、十分な効果を得ることは困難である。   On the other hand, as shown in FIG. 5, in the case of CNT 63 having a hollow structure, since atoms 51 can only enter from the tip, it is extremely difficult to achieve the same resistance reduction as graphene without increasing the diameter. That is, when applied to a hollow CNT, the doping path to the part other than the outermost CNT layer is only the tip of the CNT or a defective portion of the outer CNT, and the diameter of the CNT hardly increases. For this reason, it is difficult to dope elements stably in the CNT, and it is difficult to obtain a sufficient effect.

これに対し本実施形態では、前記図２に示すように、ＣＮＴビア３０を通常のＣＮＴではなく、グラフェンをビア用溝の深さ方向から傾けた状態で積層したカップスタックＣＮＴ３３で構成している。このため、ＣＮＴ３３の側面にグラフェンの末端が露出することになり、ＣＮＴ３３の側面から元素５１のドーピングを行うことができ、ＣＮＴビア３０の低抵抗化をはかることができる。   On the other hand, in the present embodiment, as shown in FIG. 2, the CNT via 30 is not a normal CNT, but is constituted by a cup stack CNT 33 in which graphene is stacked in a state inclined from the depth direction of the via groove. . For this reason, the end of the graphene is exposed on the side surface of the CNT 33, the element 51 can be doped from the side surface of the CNT 33, and the resistance of the CNT via 30 can be reduced.

このように本実施形態によれば、ＣＮＴビア３０を構成する各ＣＮＴ３３をカップスタック型構造としているため、ＣＮＴ３３の側面からＢｒ等の元素を効率良くドーピングすることができ、ＣＮＴビア３０の更なる低抵抗化をはかることができる。このため、ＣＮＴビア３０を用いた半導体装置において、配線抵抗の更なる低抵抗化をはかることができる。   As described above, according to the present embodiment, each CNT 33 constituting the CNT via 30 has a cup stack type structure. Therefore, an element such as Br can be efficiently doped from the side surface of the CNT 33, and the CNT via 30 can be further improved. Low resistance can be achieved. For this reason, in the semiconductor device using the CNT via 30, it is possible to further reduce the wiring resistance.

（第２の実施形態）
図６及び図７は、第２の実施形態に係わる半導体装置の製造工程を示す断面図である。 (Second Embodiment)
6 and 7 are cross-sectional views illustrating the manufacturing steps of the semiconductor device according to the second embodiment.

なお、本実施形態で作製する半導体装置は、前記図１に示す構造と同様とする。また、説明を簡単にするために、キャップ層は省略している。   The semiconductor device manufactured in this embodiment has the same structure as that shown in FIG. For the sake of simplicity, the cap layer is omitted.

まず、図６（ａ）に示すように、トランジスタやキャパシタ等の半導体素子が形成されたＳｉ基板１０上に配線層絶縁膜１２及び下地配線層１５を形成する。このとき、配線層絶縁膜１２には例えばＴＥＯＳ膜を用い、下地配線層１５の材料には例えばＷやＣｕやＡｌなどの金属を用いる。ここで、下地配線層１５は、太さ・幅共に複数種類が存在するものとする。   First, as shown in FIG. 6A, a wiring layer insulating film 12 and a base wiring layer 15 are formed on a Si substrate 10 on which semiconductor elements such as transistors and capacitors are formed. At this time, for example, a TEOS film is used for the wiring layer insulating film 12, and a metal such as W, Cu, or Al is used for the material of the base wiring layer 15. Here, it is assumed that a plurality of types of base wiring layers 15 exist in both thickness and width.

続いて、絶縁膜１２及び配線層１５上に層間絶縁膜２２を成膜する。絶縁膜２２は、例えばＳｉＯＣ膜からなり、例えばＣＶＤ法や塗布法により成膜される。この絶縁膜２２は、誘電率を下げる目的で微小空孔（Pore）を含んだ膜であっても良い。その後、図示しないレジスト塗布・リソグラフィの工程を経て、ＣＮＴビアを形成するコンタクトのみＲＩＥ加工によりビアホール２３を開孔する。   Subsequently, an interlayer insulating film 22 is formed on the insulating film 12 and the wiring layer 15. The insulating film 22 is made of, for example, a SiOC film, and is formed by, for example, a CVD method or a coating method. The insulating film 22 may be a film containing micropores (Pore) for the purpose of lowering the dielectric constant. Thereafter, via a resist coating / lithography process (not shown), the via hole 23 is opened by RIE only for the contact forming the CNT via.

次いで、図６（ｂ）に示すように、ＣＮＴの作製を容易にするための補助膜となる補助触媒層３１を、ビアホール２３内及び絶縁膜２２上に形成する。補助触媒層３１は、ビアホール底部と側面において均一に形成されることが望ましく、成膜法としては、例えばＣＶＤ法を用いれば良い。代表的な材料としては、Ｔａ，Ｔｉ，Ｒｕ，Ｗ，Ａｌなどが挙げられる。これらの膜の窒化物や酸化物、これらの膜を含む積層材料を用いることも可能である。   Next, as shown in FIG. 6B, an auxiliary catalyst layer 31 serving as an auxiliary film for facilitating the production of CNTs is formed in the via hole 23 and on the insulating film 22. The auxiliary catalyst layer 31 is desirably formed uniformly on the bottom and side surfaces of the via hole. As a film formation method, for example, a CVD method may be used. Typical materials include Ta, Ti, Ru, W, Al and the like. It is also possible to use nitrides and oxides of these films, and laminated materials including these films.

次いで、図６（ｃ）に示すように、ＣＮＴ成長のための触媒層３２を補助触媒層３１上に形成する。これにより、ビアホール２３では底部及び側壁に補助触媒層３１及び触媒層３２が形成されることになる。触媒層３２の成膜法には、例えばＣＶＤ法を用いる。触媒層３２の材料にはＣｏ，Ｎｉ，Ｆｅ、Ｒｕ、Ｃｕなどの単体金属、又は少なくともこれらの何れかを含む合金、或いはこれらの炭化物等が好ましい。触媒層３２は分散状態となる不連続膜となることが望ましい。   Next, as shown in FIG. 6C, a catalyst layer 32 for CNT growth is formed on the auxiliary catalyst layer 31. Thereby, in the via hole 23, the auxiliary catalyst layer 31 and the catalyst layer 32 are formed on the bottom and side walls. For the film formation method of the catalyst layer 32, for example, a CVD method is used. The material of the catalyst layer 32 is preferably a single metal such as Co, Ni, Fe, Ru, or Cu, an alloy containing at least one of these, or a carbide thereof. The catalyst layer 32 is preferably a discontinuous film in a dispersed state.

次いで、図７（ｄ）に示すように、電気伝導配線層となるＣＮＴ３３を形成する。ＣＮＴ３３の成膜にはＣＶＤ法を用い、炭素源にはメタン、アセチレン等の炭化水素系ガス又はその混合ガス、キャリアガスには水素や希ガスをそれぞれ使用する。ＣＮＴ３３は不連続膜となった触媒層３２上にのみ成膜されることに特徴がある。ここで、特にＣＮＴ３３の構造をグラフェン壁末端がＣＮＴ層側壁に露出した構造にするために、ＣＮＴ３３の成長時の温度・原料濃度やキャリアガス種・濃度を制御することによって制御する。これにより、前記図２に示す構造のカップスタック構造のＣＮＴ３３が得られる。特に、成長時の温度を４００℃以下にすることでカップスタック構造となり、温度を変えることでグラフェン層の高さを変えたりＣＮＴの長さ方向に対するグラフェン層の傾きを変えたりすることができる。   Next, as shown in FIG. 7D, CNTs 33 serving as an electrically conductive wiring layer are formed. A CVD method is used to form the CNT 33, a hydrocarbon gas such as methane or acetylene or a mixed gas thereof is used as the carbon source, and hydrogen or a rare gas is used as the carrier gas. The CNT 33 is characterized in that it is formed only on the catalyst layer 32 which is a discontinuous film. Here, in particular, in order to make the structure of the CNT 33 a structure in which the end of the graphene wall is exposed on the side wall of the CNT layer, the temperature, the raw material concentration, the carrier gas type and the concentration during the growth of the CNT 33 are controlled. As a result, the CNT 33 having the cup stack structure shown in FIG. 2 is obtained. In particular, when the growth temperature is set to 400 ° C. or lower, a cup stack structure is obtained. By changing the temperature, the height of the graphene layer can be changed, or the inclination of the graphene layer with respect to the length direction of the CNT can be changed.

ＣＮＴ３３の成長後は、例えばＢｒなどの原子をＣＮＴ３３へドーピングする。ドーピング元素はＢｒの他にＮ，Ｃｌなどの１４〜１７族元素が望ましく、これらの少なくとも１種を用いる。キャリアをより多く生成する目的で上記元素のうち多種を用いてもよい。   After the growth of the CNT 33, for example, atoms such as Br are doped into the CNT 33. The doping element is preferably a group 14-17 element such as N or Cl in addition to Br, and at least one of these is used. Various kinds of the above elements may be used for the purpose of generating more carriers.

本工程によるドーピングは特にフェルミエネルギーの増大によるキャリア増加を目的とした工程となっているが、更にエネルギー準位を形成する目的で、例えばＣｒ，Ｆｅ等の金属原子やそれらの錯体を用いることも可能である。   The doping in this process is a process aimed at increasing the number of carriers by increasing the Fermi energy, but for the purpose of further forming energy levels, for example, metal atoms such as Cr and Fe and their complexes may be used. Is possible.

１４〜１７族元素や金属原子、その錯体のドーピング方法としては、ＣＮＴ成長と同時の場合は、ＣＮＴをＣＶＤで成長する際、ドーピング元素を含む原料を原料ガスとして混入すれば良い。また、ＣＮＴ成長後のインターカレーションの場合は、減圧・高温下に作成したＣＮＴを含有する基板とインターカレーションに用いる元素を含む材料を同一雰囲気に晒す方法がある。例えば、室温でのドーピング元素ガスの基板への暴露や高温下、或いはプラズマ雰囲気中でのドーピングガス暴露などが挙げられる。特に、低温で十分なドーピング量を得るためには、プラズマ雰囲気中での元素ガス暴露が好ましい。また、このドーピングはＣＮＴ形成工程と同時に行ってもよい。   As a method for doping a group 14-17 element, a metal atom, or a complex thereof, in the case of CNT growth, a source material containing a doping element may be mixed as a source gas when CNT is grown by CVD. In the case of intercalation after CNT growth, there is a method in which a substrate containing CNTs produced under reduced pressure and high temperature and a material containing an element used for intercalation are exposed to the same atmosphere. For example, exposure of the doping element gas to the substrate at room temperature, doping gas exposure at a high temperature, or in a plasma atmosphere may be mentioned. In particular, in order to obtain a sufficient doping amount at a low temperature, exposure to an element gas in a plasma atmosphere is preferable. Further, this doping may be performed simultaneously with the CNT formation step.

ＣＮＴ３３の成長後は、図７（ｅ）に示すように、ＣＭＰによりフィールド領域のＣＮＴ３３、触媒層３２、及び触媒下地層３１などを除去する。この時、ＣＮＴ３３を固定化するために絶縁膜や金属などをＣＮＴ中に含浸させてもよい。   After the growth of the CNT 33, as shown in FIG. 7E, the CNT 33, the catalyst layer 32, the catalyst underlayer 31 and the like in the field region are removed by CMP. At this time, in order to immobilize the CNT 33, the CNT may be impregnated with an insulating film or a metal.

最後に、図７（ｆ）に示すように、上部配線層４５及び絶縁膜４２等を形成することにより、前記図１に示す構造が完成することになる。   Finally, as shown in FIG. 7F, the structure shown in FIG. 1 is completed by forming the upper wiring layer 45, the insulating film 42, and the like.

このように本実施形態によれば、配線抵抗の極めて低いＣＮＴビア３０を作製することができ、半導体装置におけるコンタクトビアの低抵抗化をはかることができる。また、ＣＮＴ３３の成膜条件を変えるのみで、Ｂｒ等のドーピングに適したカップスタック型のＣＮＴを作製できるので、製造プロセスの大幅な変更を要することなく実現することが可能である。   As described above, according to the present embodiment, the CNT via 30 having an extremely low wiring resistance can be manufactured, and the resistance of the contact via in the semiconductor device can be reduced. In addition, since a cup stack type CNT suitable for doping of Br or the like can be produced only by changing the film formation conditions of the CNT 33, it can be realized without requiring a significant change in the production process.

（第３の実施形態）
本実施形態では、ＣＮＴビアに用いるＣＮＴの最適構造及びその作り方について説明する。 (Third embodiment)
In the present embodiment, an optimum structure of CNT used for the CNT via and a method for making the same will be described.

第１及び第２の実施形態では、ＣＮＴビア３０をカップスタック型のＣＮＴ３３で形成している。ここで、Ｃ単元素のみから形成されたグラフェン壁末端がＣＮＴ層側壁に露出したＣＮＴは、中空構造ＣＮＴに比べて電子伝導方向のグラフェン層の長さが低いことから、中空構造よりも導電率が低くなることが知られている。他方、ドーピングによる低抵抗化への効果については、前記図３に示したグラフェンの場合と同様に、ＣＮＴの筒を開いた形状で同等の電気特性を有するグラフェンの場合で、２桁の低減効果が報告されている。   In the first and second embodiments, the CNT via 30 is formed of a cup-stacked CNT 33. Here, the graphene wall end formed from only the C single element is exposed on the side wall of the CNT layer. Since the length of the graphene layer in the electron conduction direction is lower than that of the hollow structure CNT, the conductivity is higher than that of the hollow structure. Is known to be low. On the other hand, as for the effect of reducing the resistance by doping, as in the case of the graphene shown in FIG. 3, the reduction effect of two orders of magnitude in the case of the graphene having the same electrical characteristics in the shape of the opened CNT tube Has been reported.

本構造におけるビア抵抗は上記グラフェン層の高さに起因する導電率とドーピングによる低抵抗化の効果とにより決まる。ドーピングにより抵抗が２桁低減すると仮定すると、現在のＣＮＴのターゲットとする平均自由長５００ｎｍ（これでＷプラグと同程度の抵抗）より低抵抗を実現するには、一つのグラフェン層の高さ（平均自由帳）＝５００ｎｍ／１００＝５ｎｍ以上であればよい。即ち、従来の金属ビアや中空構造ＣＮＴと同等か、それ以上の効果を有するためには、前記図２に示すように高さが５ｎｍ以上のグラフェン層をスタックすることが有効である。   The via resistance in this structure is determined by the conductivity caused by the height of the graphene layer and the effect of reducing the resistance by doping. Assuming that the resistance is reduced by two orders of magnitude by doping, in order to achieve a resistance lower than the average free length of 500 nm (which is about the same resistance as a W plug), which is the target of current CNTs, the height of one graphene layer ( Average free book) = 500 nm / 100 = 5 nm or more. That is, it is effective to stack a graphene layer having a height of 5 nm or more as shown in FIG. 2 in order to have an effect equal to or higher than that of a conventional metal via or hollow structure CNT.

このような構造を作製するためには、例えばＣＮＴの成長時の温度・原料濃度やキャリアガス種・濃度を制御することによって制御する。より具体的には、ＣＮＴの構造をグラフェン壁末端がＣＮＴ層側壁に露出したＣＮＴにするために、例えば成膜条件において温度を４００℃以下の低温に制御したり、原料を過剰に供給するなどの制御を行う。これにより、前記図２に示す構造のカップスタック構造のＣＮＴ３３が得られる。   In order to produce such a structure, for example, control is performed by controlling the temperature, raw material concentration, carrier gas species, and concentration at the time of CNT growth. More specifically, in order to make the CNT structure CNT with the graphene wall end exposed on the side wall of the CNT layer, for example, the temperature is controlled to a low temperature of 400 ° C. or less under film forming conditions, or the raw material is excessively supplied. Control. As a result, the CNT 33 having the cup stack structure shown in FIG. 2 is obtained.

（変形例）
なお、本発明は上述した各実施形態に限定されるものではない。 (Modification)
The present invention is not limited to the above-described embodiments.

ＣＮＴにドーピングする元素はＢｒに限るものではなく、ＮやＣｌを用いることも可能である。さらに、これらの複数種をドーピングしても良い。また、ＣＮＴの成膜条件は、仕様に応じて適宜変更可能であり、ＣＮＴを構成する各々のグラフェンの高さが５ｎｍ以上となる条件であれば良い。   The element for doping CNTs is not limited to Br, and N or Cl can also be used. Furthermore, you may dope these multiple types. Moreover, the film formation conditions of CNT can be suitably changed according to the specification, and may be any conditions as long as the height of each graphene constituting the CNT is 5 nm or more.

実施形態では、コンタクトビア用溝の底面及び側面に触媒層を形成したが、側面の触媒層は必ずしも必要なく、底面のみに触媒層を形成しても良い。また、実施形態では、触媒層の下地に補助触媒層を形成したが、触媒層３２から下層コンタクト中への拡散が問題とならない場合は、補助触媒層は省略することも可能である。   In the embodiment, the catalyst layer is formed on the bottom and side surfaces of the contact via groove. However, the catalyst layer on the side surface is not necessarily required, and the catalyst layer may be formed only on the bottom surface. In the embodiment, the auxiliary catalyst layer is formed on the base of the catalyst layer. However, when diffusion from the catalyst layer 32 into the lower layer contact is not a problem, the auxiliary catalyst layer can be omitted.

第２の実施形態では、ＣＮＴビアの形成後に元素のドーピングを行ったが、ＣＮＴビアの形成時に元素のドーピングを行うことも可能である。具体的には、前記図７（ｄ）に示す工程において、ＣＶＤのソースガス中にＢｒ，Ｎ，Ｃｌ等の原子を添加しておくことにより、作製されるＣＮＴ中に元素ドーピングが可能となる。ドーピングを同時に行う場合は、ドーピング元素の供給量を制御することによって、グラフェン壁末端がＣＮＴ層側壁に露出したＣＮＴを形成することが可能である。   In the second embodiment, the element doping is performed after the CNT via is formed. However, it is also possible to perform the element doping when the CNT via is formed. Specifically, in the step shown in FIG. 7D, by adding atoms such as Br, N, and Cl to the CVD source gas, element doping can be performed in the produced CNT. . When doping is performed at the same time, it is possible to form CNTs with graphene wall ends exposed on the side walls of the CNT layer by controlling the supply amount of the doping element.

本発明の幾つかの実施形態を説明したが、これらの実施形態は、例として提示したものであり、発明の範囲を限定することは意図していない。これら実施形態は、その他の様々な形態で実施されることが可能であり、発明の要旨を逸脱しない範囲で、種々の省略、置き換え、変更を行うことができる。これら実施形態やその変形は、発明の範囲や要旨に含まれると同様に、特許請求の範囲に記載された発明とその均等の範囲に含まれるものである。   Although several embodiments of the present invention have been described, these embodiments are presented by way of example and are not intended to limit the scope of the invention. These embodiments can be implemented in various other forms, and various omissions, replacements, and changes can be made without departing from the spirit of the invention. These embodiments and their modifications are included in the scope and gist of the invention, and are also included in the invention described in the claims and the equivalents thereof.

１０…Ｓｉ基板（半導体基板）
１１，２１，４１…キャップ層
１２…配線層絶縁膜
１５…下地配線層
２２…層間絶縁膜
２３…コンタクト用溝
３０…ＣＮＴビア
３１…補助触媒層
３２…触媒層
３３…ＣＮＴ
３３ａ…グラフェン層
４２…絶縁膜
４５…上部配線層
５１…元素
６１…基板
６２…グラフェン層
６３…中空構造ＣＮＴ 10 ... Si substrate (semiconductor substrate)
11, 21, 41 ... Cap layer 12 ... Wiring layer insulating film 15 ... Underlying wiring layer 22 ... Interlayer insulating film 23 ... Contact groove 30 ... CNT via 31 ... Auxiliary catalyst layer 32 ... Catalyst layer 33 ... CNT
33a ... Graphene layer 42 ... Insulating film 45 ... Upper wiring layer 51 ... Element 61 ... Substrate 62 ... Graphene layer 63 ... Hollow structure CNT

Claims (12)

第１の配線が設けられた基板と、
前記基板上に設けられ、且つ前記第１の配線に対するコンタクトビア用溝が形成された層間絶縁膜と、
前記コンタクトビア用溝の底面に形成されたカーボンナノチューブ成長のための触媒層と、
前記触媒層が形成された前記コンタクトビア用溝内に複数本のカーボンナノチューブを埋め込んで形成されたカーボンナノチューブビアと、
前記層間絶縁膜上に設けられ、前記カーボンナノチューブに接続された第２の配線と、
を具備し、
前記カーボンナノチューブは、高さが５ｎｍ以上の複数のグラフェン層を前記コンタクトビア用溝の深さ方向から傾けた状態で積層したカップスタック型の構造に形成され、且つ前記コンタクトビア用溝の側壁に前記グラフェン層の末端が露出するように形成され、前記カーボンナノチューブ中に、Ｂｒ，Ｃｌ，又はＮが含まれていることを特徴とする半導体装置。 A substrate provided with a first wiring;
An interlayer insulating film provided on the substrate and formed with a contact via groove for the first wiring;
A catalyst layer for carbon nanotube growth formed on the bottom surface of the groove for the contact vias,
A carbon nanotube via formed by embedding a plurality of carbon nanotubes in the contact via groove in which the catalyst layer is formed;
A second wiring provided on the interlayer insulating film and connected to the carbon nanotube;
Comprising
The carbon nanotube is formed in a cup stack type structure in which a plurality of graphene layers having a height of 5 nm or more are stacked in a state inclined from the depth direction of the contact via groove, and on the side wall of the contact via groove. the formed to ends of the graphene layer is exposed, said in the carbon nanotube, Br, Cl, or N semiconductor device characterized in that it contains. 基板上に設けられ、配線接続のためのコンタクトビア用溝が形成された層間絶縁膜と、
前記コンタクトビア用溝の底面に形成されたカーボンナノチューブ成長のための触媒層と、
前記触媒層が形成された前記コンタクトビア用溝内に複数本のカーボンナノチューブを埋め込んで形成されたカーボンナノチューブビアと、
を具備し、
前記カーボンナノチューブは、複数のグラフェン層を前記コンタクトビア用溝の深さ方向から傾けた状態で積層して形成され、且つ前記コンタクトビア用溝の側壁に前記グラフェン層の末端が露出するように形成され、前記カーボンナノチューブ中に少なくとも１種類の元素が含まれていることを特徴とする半導体装置。 An interlayer insulating film provided on the substrate and formed with a contact via groove for wiring connection;
A catalyst layer for carbon nanotube growth formed on the bottom surface of the groove for the contact vias,
A carbon nanotube via formed by embedding a plurality of carbon nanotubes in the contact via groove in which the catalyst layer is formed;
Comprising
The carbon nanotubes are formed by laminating a plurality of graphene layers in a state inclined from the depth direction of the contact via grooves, and formed such that the ends of the graphene layers are exposed on the side walls of the contact via grooves. is, the semiconductor device characterized in that it contains at least one element in the carbon nanotube. 前記基板に第１の配線が設けられ、A first wiring is provided on the substrate;
前記層間絶縁膜上に第２の配線が設けられ、A second wiring is provided on the interlayer insulating film;
前記カーボンナノチューブは、前記第１及び第２の配線を接続していることを特徴とする請求項２記載の半導体装置。The semiconductor device according to claim 2, wherein the carbon nanotube connects the first and second wirings. 前記グラフェン層のもう一方の末端は、前記カーボンナノチューブの中央側に位置していることを特徴とする請求項１乃至３の何れかに記載の半導体装置。4. The semiconductor device according to claim 1, wherein the other end of the graphene layer is located on a central side of the carbon nanotube. 5. 前記カーボンナノチューブに含まれた元素は、Ｂｒ，Ｃｌ，又はＮであることを特徴とする、請求項２乃至４の何れかに記載の半導体装置。 5. The semiconductor device according to claim 2 , wherein the element contained in the carbon nanotube is Br, Cl, or N. 6. 前記カーボンナノチューブは、高さが５ｎｍ以上の前記グラフェン層をスタックしたカップスタック型の構造であることを特徴とする、請求項２乃至５の何れかに記載の半導体装置。 The semiconductor device according to claim 2 , wherein the carbon nanotube has a cup-stacked structure in which the graphene layers having a height of 5 nm or more are stacked. 基板内にコンタクトビア用溝を形成する工程と、
前記溝の底面にカーボンナノチューブ成長のための触媒層を形成する工程と、
前記触媒層が形成された前記コンタクトビア用溝内に、複数のグラフェン層を該グラフェン層の末端が側壁に露出するように前記コンタクトビア用溝の深さ方向から傾けた状態で積層して複数本のカーボンナノチューブを形成し、且つ前記カーボンナノチューブに少なくとも１種類の元素をドーピングすることにより、カーボンナノチューブビアを形成する工程と、
を有し、前記カーボンナノチューブの成長を４００℃以下の温度、又は原料過剰の条件下で行うことを特徴とする特徴とする半導体装置の製造方法。 Forming a contact via groove in the substrate;
Forming a catalyst layer for carbon nanotube growth on the bottom of the groove;
The catalyst layer is formed the contact via a groove, by laminating a plurality of graphene layers in a state where end inclined from a depth direction of the contactor Tobi A groove so as to be exposed at the side wall of the graphene layer Forming carbon nanotube vias by forming a plurality of carbon nanotubes and doping the carbon nanotubes with at least one element;
And the growth of the carbon nanotubes is performed at a temperature of 400 ° C. or lower, or under an excess of raw materials . 基板上に層間絶縁膜を形成する工程と、
前記層間絶縁膜に、配線接続のためのコンタクトビア用溝を形成する工程と、
前記溝の底面にカーボンナノチューブ成長のための触媒層を形成する工程と、
前記触媒層が形成された前記コンタクトビア用溝内に、複数のグラフェン層を該グラフェン層の末端が側壁に露出するように前記コンタクトビア用溝の深さ方向から傾けた状態で積層して複数本のカーボンナノチューブを形成し、且つ前記カーボンナノチューブに少なくとも１種類の元素をドーピングすることにより、カーボンナノチューブビアを形成する工程と、
を含むことを特徴とする特徴とする半導体装置の製造方法。 Forming an interlayer insulating film on the substrate ;
Forming a contact via groove for wiring connection in the interlayer insulating film ;
Forming a catalyst layer for carbon nanotube growth on the bottom of the groove;
The catalyst layer is formed the contact via a groove, by laminating a plurality of graphene layers in a state where end inclined from a depth direction of the contactor Tobi A groove so as to be exposed at the side wall of the graphene layer Forming carbon nanotube vias by forming a plurality of carbon nanotubes and doping the carbon nanotubes with at least one element;
A method for manufacturing a semiconductor device, comprising: 前記カーボンナノチューブにドーピングする元素として、Ｂｒ，Ｃｌ，又はＮを用いることを特徴とする、請求項７又は８に記載の半導体装置の製造方法。 9. The method of manufacturing a semiconductor device according to claim 7 , wherein Br, Cl, or N is used as an element to be doped into the carbon nanotube. 前記カーボンナノチューブの成長を４００℃以下の温度、又は原料過剰の条件下で行うことを特徴とする、請求項８に記載の半導体装置の製造方法。 9. The method of manufacturing a semiconductor device according to claim 8 , wherein the growth of the carbon nanotubes is performed at a temperature of 400 [deg.] C. or less, or under an excess of raw materials. 前記カーボンナノチューブへの前記元素のドーピングを、前記カーボンナノチューブの形成の後に行うことを特徴とする、請求項７乃至１０の何れかに記載の半導体装置の製造方法。 11. The method of manufacturing a semiconductor device according to claim 7 , wherein the doping of the element into the carbon nanotube is performed after the formation of the carbon nanotube. 前記カーボンナノチューブへの前記元素のドーピングを、前記カーボンナノチューブの形成と同時に行うことを特徴とする、請求項７乃至１０の何れかに記載の半導体装置の製造方法。 11. The method of manufacturing a semiconductor device according to claim 7 , wherein the doping of the element into the carbon nanotube is performed simultaneously with the formation of the carbon nanotube.
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